Compositions and methods



COMPOSITIONS AND METHODS Harry F. Dietz, deceased, late of Chadds' Ford, Pa., by

Dorothy H. Dietz, executrix, Chadds Ford, Pa., assignor to E.'I. du Pont de' Nemours and; Company, Wilmington, DeL, acorporati'on of Delaware No Drawing. Application May 31, 1957 SerialNo. 662,950

4 Claims. (Cl. 167-22) This invention relates to certain alkyl mercury salts of polyamine acetic acids and to fungicidal compositions and methods employing these compounds for the protection of organic matter subject to fungus infection.

Recently a number of organo mercury fungicides have been made commerciallyavailable. Certain of these compounds have outstanding fungicidal activity for certain uses such as for treating seeds. However, none of these organo mercury fungicides have proven entirely satisfactory. Most of these compounds are insoluble in aqueous medium, and therefore must be formulated with some type of fungicidal adjuvant or carrier material. These few organo-mercury fungicides that are sulficiently water-soluble for application from an aqueous medium have in many cases proven to be relatively phytotoxic, and for this reason are not completely satisfactory.

It is therefore apparent that there is a real need for an improved water-soluble organomercury fungicide of high anti-fungal activity.

In accordance with the present invention, certain alkyl mercury salts of polyamine acetic acids have been discovered that are watersoluble, have high fungicidal activity, and appear to be of outstandingly low phytotoxicity at use levels.

The compounds of the present invention are alkylmercury salts of polyarnine acetic acids 'wherein the polyamine group is of the general. structure.

in which R is selected from the group consisting of divalent saturated hydrocarbon groups of from. 2'through 12 carbon atoms, and divalent saturated aliphatic chains consisting of from 4 through 12 carbon atoms and from one through 5 nitrogen atoms with each nitrogen atom dividing the chain into alkylene groups of not less than 2 carbon atoms each; at least one valence of a polyamine nitrogen being satisfied by an alkylmercury acetate group of the type 'CR R COOHgR, in which R and R uare selected from the group consisting of hydrogen and alkyl groups, and R is an alkyl group; and the remainder ofthe valences of the polyamine-nitrogens being satisfied 2,898,262 Patented Aug. 4, 1959 ice by radicals selected from the group consisting of hydrogen, alkyl groups, hydroxyalkyl groups and in which R and R have the significance set forth above and Y is selected from the group consisting of hydrogen, alkali metal cations, ammonium or substituted amine.

vThe better compounds of the present invention, from the standpoint of ease and economy of preparation and usage, are'those wherein R and R are alkyl groups containing less than 7 carbon atoms. Preferably R also contains less than 7 carbon atoms, with perhaps the best compounds being those wherein R is ethyl or methyl, and preferably ethyl.

Typical of the compounds of the present invention are the following:

1. Bis ethyl'mercury salt of ethylene diamine tetraacetic acid 2. Tetraethyl mercury salt of ethylene diamine tetraacetic acid 3. Triethylmercury salt of ethylene diamine tetraacetic acid 4.'Monoethyl mercury salt of ethylene diamine tetraacetic acid 5. Bis ethyl mercury salt of hydroxyethyl ethylene diamine triacetic acid 6. Bis ethyl mercury salt of ethylene triamine pentaacetic acid 7. Bis ethyl mercury salt of 1,2-diamino cyclohexane I tetraacetic acid 8'. Bis ethyl mercury salt of triethylene tetramine hexaacetic acid 9. Bis ethyl mercury salt of dip-ropylene triamine pentaacetic acid 10. Bis ethyl mercury salt of 1,12 dodecanediamine tetraacetic acid 11. Bis ethyl mercury salt of ditertiary butyl diamine tetraacetic acid 12. Bis ethyl mercury salt of 2,7-dimethyl-2,7-octanodiaminetetraacetic acid 13. Bis ethyl mercury salt of 1,10-decanediamine tetraacetic acid l t-Bis ethyl mercury salt of 2,2-dimethyl-1,3-propanediamine tetraacetic acid I 15.,Bis' methyl mercury salt of ethylene diamine tetraacetic acid 16. Bis propyl mercury salt of ethylene diamine tetral acetic acid 17."Bis butyl mercury salt of ethylene diamine tetraacetic acid 18. Bis heXyl .mercury salt of ethylene diamine tetraacetic acid 19. 'Methyl mercury, butyl mercury s'altof ethylene diamine tetraacetic acid The. fungicidally active compounds of the abovedescribed type can be prepared by various means. For

example, they can be prepared by reactingakpolyamine flpolyacetic-acid with'an alkyl mercury salt or' an alkyl" mercury hydroxide. They can also be prepared by reacting the polyamine polyacetic acids with mercuric oxide to form the corresponding mercuric salt and then reacting the mercuric salt with a dialkyl mercury to form the alkyl mercury salt. The polyamine polyacetic acid reactants used in these methods can be prepared by conventional means such as by reacting the polyamine with chloroacetic acid. The preparation of the polyamines themselves can be carried on by any conventional methods; many such polyamines are currently available on the market.

The above-described methods of preparing the compounds of the present invention frequently give mixtures of the mono-, di-, triand tetra-derivatives, with the relative proportions of these derivatives depending upon the reactants employed and the reaction conditions. These mixtures ordinarily are used as such in the fungicidal compositions and methods of the present invention, although they can be separated if desired.

In practicing the fungicidal methods of the present invention, one or more of the active ingredients is applied to the organic material to be treated for the control of fungi at a dosage suificient to exert fungicidal action. Accordingly, the compositions and methods of the present invention are applicable for the protection of car bohydrates, proteins and fats. They are particularly suited for the treating of living plant matter such as vegetables, ornamental plants, fruit-bearing trees, turf and seeds. Some of these compositions are also effective when applied directly to the soil for controlling plant fungi. Also they can be used to treat organic fibers and fabrics and various cellulosic materials such as leather and wood. Likewise, they can be used to treat paints and lubricating oils.

In application to plants, fungicidal control is obtained in most instances by applying the active compound at a dosage or rate from about 0.01 to 5.0 lbs/acre, the optimum amount within this range being largely de pendent upon the variables mentioned heretofore. In application directly to the soil for use as a fungicide, in most instances the dosage is from about .1 to 50 lbs./ acre. In application to seeds as a seed disinfectant, the dosage ordinarily employed is from about .01 to .1 oz./ bushel of seed. The optimum dosage can be determined in each instance by one of the means conventional in the art. It is, of course, determined by and dependent upon the particular fungicidal compound selected, the method of application, and, in the case of application to vegetation, the state and condition of growth of the vegetation to be treated and the climatic conditions.

As aforementioned, most of the compounds of the present invention are sufiiciently water-soluble to apply from an aqueous medium. This is particularly true of the alkali metal, ammonium and substituted ammonium salts. However, in some instances it is desirable to apply these fungicides in the form of a fungicidal composition. These fungicidal compositions contain in suflicient amount to exert fungicidal action one or more of the above-described active compounds in admixture with a carrier material or conditioning agent of the kind used and commonly referred to in the art as a fungicide adjuvant or modifier. The conventional fungicide adjuvants are inert solids, organic liquid diluents and surface-active agents. They provide formulations adapted for ready and efiicient application using conventional applicator equipment. Usually from about 195% by weight of the fungicidal composition is active ingredient.

Solid compositions are preferably in the form of powders. They are compounded to be homogeneous powders that can be either used as such, diluted with inert solids to form dusts, or suspended in a suitable liquid medium for spray application. The powders usually comprise active ingredient admixed with minor amounts of conditioning agent. Natural clays (either absorptive such as attapulgite or relatively non-absorptive such as kaolin clays), diatomaceous earth, walnut shell flour, tobacco dust, redwood flour, synthetic fine silica, calcium silicate and other inert solid carriers of the kind conventionally employed in powder fungicidal compositions can be used. The active ingredient usually makes up from about 25-90% of these powder compositions. For conversion of the powders to dusts, talc, pyrophyllite, tobacco dust, volcanic ash and other dense, rapid-settling inert solids customarily are used.

Liquid compositions employing one or more of the fungicidally-active ingredients are prepared by admixing the active ingredient with a suitable liquid diluent medium. The active ingredient can be either in solution or in suspension in the liquid medium. Typical of the liquid media commonly employed as fungicide adjuvants are kerosene, Stoddard solvent, xylene, alcohols, alkylated naphthalene and glycols. The active ingredient usually makes up from' about 0.5 to 50% of these,

liquid compositions. Some of these compositions are designed to be used as such, and others to be extended with large quantities of water.

Compositions in the form of wettable powders or liquids in many cases also include one or more surfaceactive agents such as Wetting, dispersing or emulsifying agents. These materials cause the compositions to disperse or emulsify easily in water to give aqueous sprays.

The surface-active agents employed can be of the anionic, cationic or nonionic type. They include, for example, sodium oleate, sulfonated petroleum oils, alkyl aryl sulfonates, sodium lauryl sulfate, polyethylene oxides, lignin sulfonates, and other surface-active agents. A detailed list of such agents is set forth in an article by McCutcheon in Soap and Chemical Specialties, volume 31 Nos. 7-10 (1955).

In some cases it may be desirable to employ the active compounds of the present invention in combination with other fungicides to give compositions that have broad spectrum fungicidal activity. In these mixtures, the fungicidally active materials can be present in any desired amount, ordinarily from about 01-20 parts by weight of a compound represented by Formula 1 per part by weight of the auxiliary fungicidally active material. In some instances it may even be desirable to employ two or more auxiliary fungicides.

Typical of the auxiliary fungicides that can be employed in combination with the compounds of the present invention are the following:

Manganese dimethyl dithiocarbamate plus 2-mercaptobenzothiazole Copper dihydrazinium sulfate Copper-S-quinolinolate Cycloheximide Terramycin Stereptomycin Also insecticides such as aldrin, dieldrin, endrin,

heptachlor and chlordane can be included in these compositions.

In order that the invention may be better understood,

escapee Example 1 Fifty grams of ethylene diamine tetraacetic acid are made into apaste withwater and then 37.05 grams of mercuric oxide are added to the paste and mixed well. The mixture is warmed on a steam bath'andstirred constantly for several hours during which time the yellow color of the mercuric oxide disappears and the composition turns entirely White. This monomercury derivative of ethylene diamine tetraacetic acid is made into a thin slurry with 300 ml. of methanol and then 44.2 grams of mercury diethyl is added slowly while stirring. During the addition of the mercury diethyl, the mixture thickens and more methanol is added to maintain a thin slurry. After all of the mercury diethyl has beenadded; the reaction mixture is warmed on a steam bath for several hours and is then allowed to-evaporate to dryness. After drying to constant weight, the white crystals of his ethyl mercury salt of ethylene diamine tetraacetic acid weigh 127 grams (100% yield equals 128.5 grams). The compound is slightly soluble in Water, highly soluble in aqueous solutions of sodium hydroxide and ammonia, and after recrystallization from water gives a compound that softens at 141 C. and darkens on further heating.

Example 2 Fifteen grams of ethyl mercury acetate are dissolved in 200 ml. of water and then 7.6 grams of ethylene diamine tetraacetic acid are added in small portions at a time while warming the reaction mixture on a steam bath. At first the mixture forms a clear solution indicating some water solubility of the compound formed. When more of the ethylene diamine tetraacetic acid is added a crystalline product forms. After all of the ethylene diamine tetraacetic acid has been added the reaction mixture is warmed on the steam bath to complete the reaction. The aqueous portion is allowed to evaporate until about 100 ml. of water remains. The mixture is then cooled and the white crystals are filtered, washed with water and dried. 17.5 grams of white crystals are obtained. The compound obtained is his ethyl mercury salt of ethylene diamine tetraacetic acid. These crystals are slightly soluble in water and highly soluble in aqueous solutions of NaOH and NH Example 3 The tetraethyl mercury salt of ethylene diamine tetraacetic acid is prepared by reacting the dimercury salt of ethylene diamine tetraacetic acid with mercury diethyl as follows:

.Ten grams of ethylene diamine tetraacetic acid are mixed with 14.8 grams of mercuric oxide and then made into a paste by the addition of water. The mixture is warmed in a steam bath for several hours while being stirred. The yellow color of the mercuric oxide disappears and the reaction mixture becomes white. 17.7 grams of mercury diethyl are then added slowly to the water slurry of the dimercury derivative of ethylene diamine tetraacetic acid. A reaction takes place immedi ately as is evidenced by a rise in temperature. After all of the mercury diethyl has been added the mixture is held at about 60 C. for one hour and then finally heated to 80 C. until dry. 41 grams of a white crystallinecompound are obtained. This compound is slightly soluble in water but very soluble in aqueous solutions of ammonia. Recrystallization from water gives a compound that softens at 129 C. but darkens on further heating.

Example 4 In accordance with the procedure of Example. 2, the compounds given in the following table are made by reacting one mole of the amino acetic acid with the in dicated number of moles of the alkylmercury acetate:

Compound Amino Acetic Acid Alkyl Mercury Acetate trlethyl mercury salt of ethethylene diamine 3 moles ethyl yleie diamine tetraacetic tetraacetic acid. mercury acetate. aci

monoethyl mercury salt of do 1 mole ethyl ethylene diamine tetramercury acetate. acetic acid.

bis ethyl mercury salt of hydroxy ethyl eth- 2 moles ethyl hydroxyethyl ethylene diamine triacetic acid.

Bis ethyl mercury salt of ethylene triamine pentaacetlc acid.

ylene diamine triacetic acid. ethylene triamine pentaacetic acid.

mercury acetate.

Bis ethyl mercury salt of 1, 2-diamino cyclo- Do.

1, 2-diamino cyclohexane hexane tetraacetic tetraacetic acid. acid.

Bis ethyl mercury salt of triethylene'tetra- Do.

triethylene tetramine mine hexaacetic hexaacetic acid. acid.

Bis ethyl mercury salt-of- -dipropylene tria- 'Do.

dipropylene triamine penmine pentaacetic taacetic acid. acid.

bis ethyl mercury salt of 1-12 dodecanedia- D0.

1-12 dodecanediamine mine tetraacetic tetraacetic acid. 'ac

bis, ethyl mercury salt of ditertiary butyldia- Do.

ditertiary butyl diamine mine tetraacetic tetraacetic acid. acid.

bis ethyl mercury salt of 2,7-dimethyl-2, 7- Do.

2, 7-dimethyl-2, 7-0ctane octane diamine diamine tetraacetic acid. tetraacetic acid.

bis ethyl mercury salt of 1,l0-decanedia- Do.

1, 10 decanediamine tetramine tetraacetic acetic Salt. acid.

bis ethyl mercury salt of 2, 2-dimethyl-1, 3- D0.

2, 2-dimethyl-1, 3-propropane diamine patediamine tetraacetic tetraacetic acid. aci

bis methyl mercury salt of ethylene diamine 2 moles methyl et ylene diamine tetratetraacetic acid. mercury acetate. acetic acid.

bis propyl mercury salt of do 2 moles propyl ethylene diamine tetramercury acetate. acetic acid.

bis butyl mercury salt of do 2moles butyl mer ethylene diamine tetracury acetate. acetic acid.

bis hexyl mercury salt of .-do 2moles hexyl merethylene diamine tetracury acetate. acetic acid.

methylmercury,butylmer- .-do lmolemethylmercury salt of ethylene dicury acetate and amine tetraacetic acid. lmole butyl mercury acetate.

Example 5 The following aqueous formulations are prepared by stirring the listed ingredients together. tions are suitable for application using conventional seed These composi- These compositions, when applied to wheat, rye and oat seeds at the rate of /2 oz. of the active ingredients per bushel, give excellent protection to the seed against fungus attack.

Example 6 The following dust formulations are prepared by blending the listed ingredients and grinding them to a particle size substantially less than 20 microns.

G. Bis ethyl mercury derivative of ethylene diamine tetraacetic acid 5.0 Dusting talc 95.0

Bis ethyl mercury salt of ethylene diamine tetraacetic acid 25.0 Attapulgite clay 75.0

Tetraethyl mercury derivative of ethylene diamine tetraacetic acid 10.0 Dusting talc 45.0 Diatomaceous earth 45.0

Bis ethyl mercury salt of hydroxyethyl ethylene diamine triacetic acid 5.0 Dusting talc 47.5 China clay 47.5

Bis ethyl mercury salt of diethylene triamine pentaacetic acid 5.0 Dusting talc 95.0

Monoethyl mercury salt of ethylene diamine tetraacetic acid 10.0 Pyrophyllite 90.0

These compositions, when applied to Wheat seed, give excellent disinfectant action. The formulations containing active are applied at the rate of V2 oz./bu.; the formulations at oz./bu.; and the 25% formulation at .1 oz/bu.

Example 7 The following dispersible powder formulations are prepared by blending together the listed ingredients and grinding to a particle size substantially less than 10 microns.

G. Tetraethyl mercury derivative of ethylene diamine tetraacetic acid 4.1 Sodium lignin sulfonate 2.0 Alkyl aryl sodium sulfonate 1.0 China clay 92.9

Bis ethyl mercury salt of ethylene diamine tetraacetic acid 10.0 Sodium lignin sulfonate 3.0 Sodium lauryl sulfate 0.5 Attapulgite clay 86.5

Bis ethyl mercury salt of hydroxy ethyl ethylene diamine triacetic acid 40.0 Sodium naphthalene sulfonate-formaldehyde condensation product 1.0 Alkyl aryl polyether alcohol 1.0 Diatomaceous earth 58.0

Mono ethyl mercury salt of ethylene diamine tetra- These compositions when applied as a spray to apple foliage 48 hours after infection by apple scab (Venturia inaequalis) will effect a cure of infection. The 10% active formulation is used at a rate of to 4 pound per gallons and the other formulations are used at equivalent rates of active ingredient. For example, only as much of the 40% formulation would be required to give the same amount of active ingredient as the 10% formulation.

What is claimed is:

1. The method for the control of fungi on plants, seeds, leather, wood, organic fabrics and fibers, and in soil, paints, and lubricating oils, comprising applying to a said material to be protected an alkyl mercury salt of polyamine acetic acid wherein the polyamine group is represented by the structure in Which R is selected from the group consisting of divalent saturated hydrocarbon groups of from 2 through 12 carbon atoms and divalent saturated aliphatic chains consisting of from 4 through 12 carbon atoms and from one through 5 nitrogen atoms with each nitrogen atom dividing the chain into alkylene groups of not less than 2 carbon atoms each; from 1 through 4 valences of the polyamine nitrogens being satisfied by an alkylmercury acetate group of the type CR R COOHgR in which R and R are selected from the group consisting of hydrogen and alkyl groups of less than 7 carbon atoms, and R is an alkyl group; and the remainder of the valences of the polyamine nitrogens being satisfied by radicals selected from the group consisting of hydrogen, alkyl groups of less than 7 carbon atoms, hydroxyalkyl groups of less than 7 carbon atoms and -CR R COOY in which R; and R have the significance set forth above and Y is selected from the group consisting of hydrogen, alkali metal cations, ammonium or substituted amine.

2. A fungicidal composition comprising a fungicidal adjuvant, and an alkyl mercury salt of polyamine acetic acid wherein the polyamine group is represented by the structure in which R is selected from the group consisting of divalent saturated hydrocarbon groups of from 2 through 12 carbon atoms and divalent saturated aliphatic chains consisting of from 4 through 12 carbon atoms and from one through 5 nitrogen atoms with each nitrogen atom dividing the chain into alkylene groups of not less than 2 carbon atoms each; from 1 through 4 valences of the polyamine nitrogens being satisfied by an alkyl mercury acetate group of the type CR R COOHgR in which R and R are selected from the group consisting of hydrogen and alkyl groups of less than 7 carbon atoms, and R is an alkyl group of less than 7 carbon atoms; and the remainder of the valences of the polyamine nitrogens being satisfied by radicals selected from the group consisting of hydrogen, alkyl groups of less than 7 carbon atoms, hydroxyalkyl groups of less than 7 carbon atoms and CR R COOY in Which R and R have the significance set forth above and Y is selected from the group consisting of hydrogen, alkali metal cations, ammonium or substituted amine.

3. A fungicidal composition comprising a water-glycolalcohol solution of an alkyl mercury salt of polyamine acetic acid wherein the polyamine group is represented by the structure.

in which R is selected from the group consisting of divalent saturated hydrocarbon groups of from 2 through 12 carbon atoms and divalent saturated aliphatic chains consisting of from 4 through 12 carbon atoms and from one through 5 nitrogen atoms with each nitrogen atom dividing the chain into alkylene groups of not less than 2 carbon atoms each; from 1 through 4 valences of the polyamine nitrogens being satisfied by an alkyl mercury acetate group of the type -CR R COOHgR in which R and R are selected from the group consisting of hydrogen and alkyl groups of less than 7 carbon atoms, and R is an alkyl group of less than 7 carbon atoms; and the remainder of the valences of the polyamine nitrogens being satisfied by radicals selected from the group consisting of hydrogen, alkyl groups of less than 7 carbon atoms, hydroxyalkyl groups of, less than 7 carbon atoms and -CR R COOY in which R and R have the significance set forth above and Y is selected from the group consisting of hydrogen, alkali metal cations, ammonium or substituted amine.

4. A fungicidally active compound represented by the formula \NR1-N/ in which R is selected from the group consisting of divalent saturated hydrocarbon groups of from 2 through 12 carbon atoms and divalent saturated aliphatic chains consisting of from 4 through 12 carbon atoms and from one through 5 nitrogen atoms with each nitrogen atom dividing the chain into alkylene groups of not less than 2 carbon atoms each; from 1 through 4 valences of the polyamine nitrogens being satisfied by an alkyl mercury acetate group of the type --CH R COOHgR in which R and R are selected from the group consisting of hydrogen and alkyl groups of less than 7 carbon atoms, and R is an alkyl group of less than 7 carbon atoms; and the remainder of the valences of the polyamine nitrogens being satisfied by radicals selected from the group consisting of hydrogen, alkyl groups of less than 7 carbon atoms, hydroxyalkyl groups of less than 7 carbon atoms and CR R COOY in which R and R have the significance set forth above and Y is selected from the group consisting of hydrogen, alkali metal cations, ammonium or substituted amine.

References Cited in the file of this patent UNITED STATES PATENTS Kharasch July 15, 1930 OTHER REFERENCES UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Noo 2,898,262 August 4: 1959 I'Iarry F0 Dietz, deceased, by Dorothy Diet-z, executrix It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should readas corrected below.

Column 8, line 39, after group" insert of less than 7 carbon atoms column 10, line 9, for -CI-I R CGOHg R P read =GR R COOHgR Signed and sealed. this 9th day of 1960.,

(SEAL?) Attest:

KARL 1 1d AXLINE ROBERT C. WATSON Attesting Oflicer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION August 4, 1959 Liarry F :ietz, deceased, by Dorothy 5., llietz, executrix It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 8, line 39, after gzrroup" insert of less than 7 carbon atoms column 10, line- 9, for "43l-E;R OOOI Ig.R read =GR R COOHgR Signed and sealed this 9th day of 196D,

(SEAL) Attest:

KARL EL, MILINE ROBERT C. WATSON Attesting Ofiicer Commissioner of Patents 

2. A FUNGICIDAL COMPOSITION COMPRISING A FUNGICIDAL ADJUVANT, AND AN ALKYL MERCURY SALT OF POLYAMINE ACETIC ACID WHEREIN THE POLYAMINE GROUP IS REPRESENTED BY THE STRUCTURE 